5-amino or substituted amino 1,2,3-triazoles

ABSTRACT

Novel 5-amino or substituted amino 1,2,3-triazoles are disclosed as having anticoccidial activity. The compounds are useful for controlling coccidiosis when administered in minor quantities to animals, in particular to poultry, usually in admixture with animal sustenance.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of our copending applicationSer. No. 576,302 filed Feb. 2, 1984 now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to new chemical compounds and the method of thepreparation of the same. It relates further to the use of such newcompounds for treating and preventing coccidiosis. This invention stillmore particularly relates to novel 5-amino and substituted amino1,2,3-triazole compounds and substituted derivatives thereof and the useof the same in the control and treatment of coccidiosis.

Coccidiosis is a wide-spread poultry disease which is produced byinfections of protozoa of the genus Eimeria which causes severepathology in the intestines and ceca of poultry. Some of the mostsignificant of these species are E. tenella, E. acervulina, E. necatrix,E. brunetti, E. maxima, E. mitis, E. mivati, E. hagani and E. praecox.This disease is generally spread by the birds picking up the infectiousorganism in droppings on contaminated litter or ground or by way of foodor drinking water. The disease is manifested by hemorrhage, accumulationof blood in the ceca, passage of blood to the droppings, weakness anddigestive disturbances. The disease often terminates in the death of theanimal but the fowl which survive severe infections have had theirmarket value substantially reduced as a result of the infection.Coccidiosis is therefore a disease of great economic importance andextensive work has been done to find new and improved methods forcontrolling and treating coccidial infections in poultry.

SUMMARY OF THE INVENTION

This invention is based on the discovery that certain novel 5-amino andsubstituted amino 1,2,3-triazoles as well as substituted derivativesthereof have a surprisingly and unexpectedly high degree of activityagainst coccidiosis of poultry. Administration of a small amount of atleast one of these compounds preferably by combination with poultry feedis effective in preventing or greatly reducing the incidence ofcoccidiosis. The compounds are effective against both the cecal form(caused principally by E. tenella) and the intestinal forms (principallycaused by E. acervulina, E. brunetti, E. maxima and E. necatrix). Thecoccidiostats of this invention are particularly effective against thespecies that cause cecal damage in addition to preventing the pathologycaused by the coccidia.

The instant compounds are also active against Eimeria spp, in otheranimals.

The 1,2,3-triazole derivatives may be prepared by reacting appropriatelysubstituted nitriles with appropriately substituted azides in thepresence of a base in a suitable reaction medium to obtains such novel5-amino-1-substituted-1,2,3-triazoles.

Some of the novel 1,2,3-triazole derivatives of this invention may alsobe prepared by reacting an appropriately substituted halide and a1-unsubstituted 1,2,3-triazole compound in the presence of a base in asuitable reaction medium to obtain such novel 5-amino or substitutedamino 1-substituted 1,2,3-triazoles.

The novel 1,2,3-triazole derivatives of this invention may also beprepared by reaction of a 1-substituted 5-amino-1,2,3-triazole compoundwith an appropriately substituted halide in the presence of a base in asuitable reaction medium to obtain such novel1-substituted-5-substituted amino 1,2,3-triazoles.

It is therefore a primary object of this invention to provide novel5-amino or substituted amino 1,2,3-triazoles with appropriatesubstitutions at the 1, 4 and 5-positions which are useful in thecontrol of coccidiosis. Still another object of this invention is toprovide novel feed compositions useful for the prevention andsuppression of coccidiosis. A further object of this invention is toprovide a new and useful method for the control of coccidiosis inpoultry which comprises administering to the poultry minor amounts ofthe anti-coccidial substance of this invention. A still further objectof this invention is to provide a method and alternate methods forpreparing novel 5-amino and substituted amino 1,2,3-triazoles. These andfurther objects of this invention will become apparent from reading thefollowing description.

DESCRIPTION OF THE INVENTION

The novel compounds of this invention are best realized in the followingstructural formula: ##STR1## wherein: ##STR2## wherein one of R, R' andR" is trichlorovinyl and the other two of R, R' and R" are selected fromhydrogen, halogen, cyano, trifluoromethyl, loweralkanoyl, nitro,loweralkyl, loweralkoxy, carboxy, carbalkoxy, trifluoromethoxy,acetamido, loweralkylthio, loweralkylsulfinyl, loweralkylsulfonyl,trichlorovinyl, trifluoromethylthio, trifluoromethylsulfinyl, ortrifluoromethylsulfonyl;

R₂ is amino, mono or diloweralkyl amino, acetamido, acetimido, ureido,formamido, formimido or guanidino; and

R₃ is carbamoyl, cyano, carbazoyl, amidino or N-hydroxycarbamoyl.

The preferred novel compounds of the instant invention are realized inthe above structural formula when one of R, R' and R" is trichlorovinyland the other two of R, R' and R" are selected from hydrogen, halogen,cyano, trifluoromethyl, trichlorovinyl or methyl;

R₂ is amino; and

R₃ is carbamoyl.

Further preferred compounds of this invention are realized where R istrichlorovinyl, R' is hydrogen and R" is selected from halogen, cyano,trifluoromethyl or methyl.

The most preferred compounds of this invention are realized when R istrichlorovinyl and R' is hydrogen and R" is halogen or trifluoromethyl.

Examples of the preferred novel compounds of this invention are:

5-amino-1-[3-chloro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-(4-trichlorovinylbenzyl)-1,2,3-triazole-4-carboxamide;

5-amino-1-[3-bromo-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[3-fluoro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[3-trifluoromethyl-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[3,5-di(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[3-chloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[4-chloro-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide;

5-amino-1-[3,5-dichloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.

A further aspect of this invention involves the use of the above novelcompounds, and other structurally related compounds in novelcompositions and methods for the treatment of coccidiosis. The novelcompositions and methods of this invention, which include the abovenovel compounds, are best realized in the following structural formula:##STR3## wherein:

R₁ is phenyl, phenyl loweralkyl, substituted phenyl or substitutedphenyl loweralkyl wherein the substituents are 1 to 5 of halogen, cyano,trifluoromethyl, loweralkanoyl, nitro, loweralkyl, loweralkoxy, carboxy,carbalkoxy, trifluoromethoxy, acetamido, loweralkylthio,loweralkylsulfinyl, loweralkylsulfonyl, trichlorovinyl,trifluoromethylthio, trifluoromethylsulfinyl, ortrifluoromethylsulfonyl;

R₁ may also be phenacyl, pyridyl, pyridylmethyl, naphthyl,naphthylmethyl, quinolyl or quinolylmethyl; and

R₂ and R₃ are as defined above.

The preferred compounds forming the active ingredient in the novelcompositions and methods of the instant invention are realized in theforegoing structural formula wherein:

R₁ is mono- di- or tri-substituted phenyl or mono- di- ortri-substituted benzyl wherein the substituents are halogen, cyano,trifluoromethyl, trichlorovinyl or methyl;

R₂ is amino; and

R₃ is carbamoyl.

The most preferred compounds of the instant novel compositions andmethods of the instant invention are realized in the foregoingstructural formula wherein R₁ is di- or tri-substituted phenyl or di- ortri-substituted benzyl, and wherein the substituents are in the meta orpara positions and are chloro, cyano, methyl, trifluoromethyl, ortrichlorovinyl;

R₂ is amino; and

R₃ is carbamoyl.

Examples of preferred compounds of the novel compositions and methods ofthis invention are, in addition to the specific compounds named above:

5-amino-1-(3,4-dichlorobenzyl)-1,2,3-triazole-4-carboxamide,

5-amino-1-(3,4,5-trichlorobenzyl)-1,2,3-triazole-4-carboxamide,

5-amino-1-(4-chloro-3-trifluoromethylbenzyl)-1,2,3-triazole-4-carboxamide,

In the instant invention the term "loweralkyl" is intended to includethose alkyl groups containing from 1 to 3 carbon atoms. Exemplary ofsuch groups are methyl, ethyl, propyl and isopropyl.

The term "loweralkoxy" is intended to include those alkoxy groupscontaining from 1 to 3 carbon atoms. Exemplary of such groups aremethoxy, ethoxy, propoxy, and isopropoxy.

The term "loweralkanoyl" is intended to include those alkanoyl groupscontaining 1 to 3 carbon atoms exemplified by formyl, acetyl, andpropionyl.

The compounds of the instant invention may be prepared by any one ofseveral processes. The most general process is outlined in the followingreaction scheme.

Reaction Scheme I: ##STR4## wherein an R₃ -methylene substituted nitrileis allowed to react with an R₁ substituted azide in the presence of abase to provide the desired 5-amino-1-substituted-1,2,3-triazole. Thereaction is carried out in solvents such as aromatic hydrocarbons, loweralkanols, dimethylformamide, dimethylsulfoxide or hexamethylphosphorictriamide. The base may be any alkali metal or alkaline earth hydroxide,alkoxide or hydride such as sodium ethoxide, potassium t-butoxide,magnesium ethoxide, sodium hydroxide or sodium hydride, chosen to becompatible with the reaction solvent. Generally the reaction isconducted at from -40° C. to 100° C. and is complete in from 15 minutesto 48 hours. The product of the reaction is isolated by techniques knownto those skilled in the art.

Reaction Scheme II ##STR5## wherein X is a halogen, preferably chlorineor bromine. In the foregoing reaction a 1-unsubstituted but otherwiseappropriately substituted 1,2,3-triazole is reacted with a halogensubstituted R₁ group in the presence of a base to prepare the desired1-substituted 1,2,3-triazole. The reaction is carried out in a solventwhich may be any polar aprotic organic solvent such asdimethylformamide, dimethylsulfoxide, acetonitrile, dioxane, and thelike in the presence of a base. The base may be any non-nucleophilicorganic or inorganic base. Suitable inorganic bases are alkali metalbases, such as sodium and potassium carbonates, phosphates, bicarbonatesand hydroxides, or sodium hydride, chosen for compatibility with thereaction solvent. Suitable organic bases are tertiary amines such astrialkyl substituted amines. The reaction rate varies greatly with thenature of the proposed substituent at the R₁ position, the base beingused in the reaction and the solvent. Very reactive substituent and basecombinations may be complete in as little as ten minutes and at theother extreme the reaction may take as long as two weeks. Most reactionsare however complete in from 1 to 100 hours. The reaction is carried outat a temperature of from room temperature to 100° C. or to the refluxtemperature of the solvent system being used. The products of thereaction are isolated using techniques known to those skilled in theart.

The novel compounds of this invention are orally administered to poultryfor the control and prevention of coccidiosis. Any number ofconventional methods are suitable for administering the coccidiostats ofthis invention to poultry, as for example, they may be given in thepoultry feed. The actual quantity of the coccidiostats administered tothe poultry in accordance with this invention will vary over a widerange and be adjusted to individual needs, depending upon species of thecoccidia involved and severity of the infection. The limiting criteriaare that the minimum amount is sufficient to control coccidiosis and themaximum amount is such that the coccidiostat does not cause anyundesirable effects.

A feed typically contains from about 0.001 to about 0.2 percent,preferably from about 0.003 to about 0.1 percent, by weight of one ofthe coccidiostats of this invention. The optimum levels will naturallyvary with the specific compound utilized and species of Eimeriainvolved, and can be readily determined by one skilled in the art.Levels of the 5-amino and substituted amino 1,2,3-triazoles of thisinvention, in poultry feed of from about 0.003 percent to about 0.1percent by weight of the diet are especially useful in controlling thepathology associated with E. tenella, as well as the intestinal dwellingspecies.

Depending on the compound employed, levels as low as 0.001 percentpossess the novel effects of reducing the number of oocysts passed inthe droppings of infected chickens.

The quantity or concentration of a novel coccidiostat of this inventionin any admixture in which it is administered to the poultry will, ofcourse, vary in accordance with the type of admixture utilized.

Of the various methods of administering the coccidiostats of thisinvention to poultry, they are most conveniently administered as acomponent of a feed composition. The novel coccidiostats may be readilydispersed by mechanically mixing the same in finely ground form with thepoultry feedstuff, or with an intermediate formulation (premix) that issubsequently blended with other components to prepare the final poultryfeedstuff that is fed to the poultry. Typical components of poultryfeedstuffs include molasses, fermentation residues, corn meal, groundand rolled oats, wheat shorts and middlings, alfalfa, clover and meatscraps, together with mineral supplements such as bone meal and calciumcarbonate and vitamins.

The following non-limiting examples will serve to further illustrate theinstant invention.

EXAMPLE 1 5-Amino-1-(3,4-dichlorobenzyl)-1,2,3-triazole-4-carboxamide

Method A

A stirred mixture of 3,4-dichlorobenzyl chloride (12.6 g, 64.5 mmol) andsodium azide (7.0 g, 0.11 mole) in absolute ethanol (70 ml) was refluxedfor 4.75 hours, cooled and filtered to provide a solution of3,4-dichlorobenzyl azide. Separately, 2-cyanoacetamide (5.5 g, 65 mmol)was added to a 35° C. solution of sodium (1.5 g, 65 mmol) in absoluteethanol (125 ml), and to the resulting suspension was added the aboveazide solution dropwise over 10 minutes. The combined mixtures wererefluxed for 1 hour, kept 16 hours at ambient temperature and 1 hour at5° C., and filtered. The crude product was dried under vacuum, dissolvedin boiling ethanol (290 ml), filtered hot, and cooled to 0° C. The solidwas collected by filtration and dried under vacuum to provide 12.4 g(67%) of 1-(3,4-dichlorobenzyl)-5-amino-1,2,3-triazole-4-carboxamide,m.p. 221°-222° C.

Method B

A stirred, ambient temperature solution of5-amino-1,2,3-triazole-4-carboxamide (635 mg, 5.00 mmole) in drydimethylformamide (20 ml) is treated in one portion with sodium hydride(240 mg of a 50% dispersion in mineral oil, 120 mg NaH, 5.0 mmol). After15 min 3,4-dichlorobenzyl chloride (0.977 g, 5.00 mmol) is added. Themixture is stirred 1 hour, poured into water (20 ml), acidified to pH 6with glacial acetic acid, and filtered. The solid is washed with water,dried, and chromatographed to provide5-amino-1-(3,4-dichlorobenzyl)-1,2,3-triazole-4-carboxamide.

EXAMPLE 2 5-Amino-1-(4-methylbenzyl)-1,2,3-triazole-4-carboxamide

A stirred mixture of 4-methylbenzyl bromide (1.3 g, 7.0 mmol) and sodiumazide (754 mg, 11.6 mmol) in ethanol (8 ml) was refluxed under anitrogen atmosphere for 3 hours, cooled to ambient temperature, andfiltered. Separately, 2-cyanoacetamide (588 mg, 7.0 mmol) was added to astirred, refluxing solution of sodium (167 mg, 7.2 mmol) in ethanol (15ml), followed by dropwise addition of the above azide solution over 20min. The resulting slurry was PG,15 refluxed 1 hour, cooled to ambienttemperature, and refrigerated. The precipitate was collected byfiltration, washed with ethanol, and dried under vacuum to provide 1.12g (69%) of 1-(4-methylbenzyl)-5-amino-1,2,3-triazole-4-carboxamide, m.p.223°-225° C.

EXAMPLE 3 4-Chloro-3-cyanobenzyl bromide

A mixture of 2-chloro-5-methylbenzonitrile (10.6 g, 69.9 mmol),N-bromosuccinimide (12.2 g, 68.5 mmol), and dibenzoyl peroxide (349 mg,1.44 mmol) in benzene (350 ml) was refluxed 1.5 hours, cooled, andevaporated to dryness under vacuum. The residue was suspended in 7:3(v/v) hexane-dichloromethane, filtered, and evaporated. The crudeproduct was chromatographed on silica gel (650 g) eluted with 7:3 (v/v)hexane-dichloromethane to provide 4.8 g (30%) 4-chloro-3-cyanobenzylbromide, m.p. 55°-58° C.

EXAMPLE 4 4-Chloro-3-cyanobenzyl azide

A stirred mixture of 4-chloro-3-cyanobenzyl bromide (3.0 g, 13 mmol) andsodium azide (1.26 g, 19.4 mmol) was refluxed 5 hours in absoluteethanol (30 mL). The mixture was kept 18 hours at ambient temperature,filtered, and the filtrate was evaporated under vacuum. The residue wastriturated with diethyl ether, filtered, and evaporated to provide 2.45g (98%) liquid 4-chloro-3-cyanobenzyl azide; I.R. (neat): 2240, 2100cm¹.

EXAMPLE 55-Amino-1-(4-chloro-3-cyanobenzyl)-1,2,3-triazole-4-carboxamide

A stirred suspension of 2-cyanoacetamide (790 mg, 9.40 mmol) in absoluteethanol (40 ml) was treated with sodium methoxide (495 mg, 9.16 mmol)and refluxed 10 minutes. The mixture was cooled slightly, a solution of4-chloro-3-cyanobenzyl azide (1.35 g, 7.01 mmol) in absolute ethanol (10ml) was added in one portion, and the mixture was refluxed 2.5 hours.The mixture was filtered hot, the solid was washed with absoluteethanol, and the combined filtrate and wash were evaporated to drynessunder vacuum. The residue was triturated with diethyl ether, filtered,and washed twice with diethyl ether. The solid was recrystallized frommethanol (6 ml) and dried at 65° C. under vacuum to provide 635 mg (24%)5-amino-1-(4-chloro-3-cyanobenzyl)-1,2,3-triazole-4-carboxamide, m.p.172°-175° C.

EXAMPLE 61-(3,4-Dichlorobenzyl)-5-methylamino-1,2,3-triazole-4-carboxamide

A mixture of 5-amino-1-(3,4-dichlorobenzyl)-1,2,3-triazole-4-carboxamide(2.86 g, 10.0 mmol), methyl iodide (1.42 g, 10.0 mmol), and potassiumcarbonate (1.38 g, 10.0 mmol) in N,N-dimethylformamide (20 ml) isstirred 48 hours at ambient temperature, poured into water (150 ml), andfiltered. Chromatography provides1-(3,4-dichlorobenzyl)-5-methylamino-1,2,3-triazole-4-carboxamide.

EXAMPLE 75-Amino-1-(4-chloro-3-cyanobenzyl)-1,2,3-triazole-4-carboxamide

A stirred suspension of 2-cyanoacetamide (790 mg, 9.4 mmol) in absoluteethanol (40 ml) was treated with sodium methoxide (495 mg, 9.2 mmol) andrefluxed 10 minutes. The mixture was cooled lightly, a solution of4-chloro-3-cyanobenzyl azide (1.35 g, 7.0 mmol) in absolute ethanol wasadded, and the mixture was refluxed 2.5 hours. The mixture was filteredhot and the filtrate evaporated under vacuum. The residue was trituratedwith diethyl ether, filtered and washed twice with diethyl ether. Thesolid was crystallized from refluxing methanol, filtered, washed twicewith methanol and once with diethyl ether, and dried at 65° C. undervacuum to provide 635 mg (33%)5-amino-1-(4-chloro-3-cyanobenzyl)-1,2,3-triazole-4-carboxamide, m.p.172°-175° C.

EXAMPLE 85-Amino-1-(4-cyano-3,5-dichlorobenzyl)-1,2,3-triazole-4-carboxamide

A stirred, ambient temperature solution of5-amino-1,2,3-triazole-4-carboxamide (630 mg, 5.0 mmol) in dryN,N-dimethylformamide (20 ml) was treated with sodium hydride (250 mg ofa 50% dispersion in mineral oil, 125 mg NaH, 5.2 mmol). The resultingsuspension was stirred 10 min., 4-cyano-3,5-dichlorobenzyl chloride (1.1g, 5.0 mmol) was added, and the mixture was stirred 2 hours. Thereaction was quenched by pouring into ice and water (80 ml). Thesuspension was filtered and washed three times with water. The solid wassuspended in 19:1 (v/v) dichloromethane-methanol and filtered to provide364 mg (23%)5-amino-1-(4-cyano-3,5-dichlorobenzyl)-1,2,3-triazole-4-carboxamide.Recrystallization from ethanol provided material of m.p. 238°-239.5° C.

EXAMPLE 9 3-Chloro-5-methylbenzyl bromide

A solution of 5-chloro-m-xylene (59.3 g) and dibenzoyl peroxide (5.0 g)in 1.13 L of benzene was heated at reflux. N-Bromosuccinimide (82.2 g)was added in portions over 15 minutes. Heating was continued for anadditional 20 minutes until a negative potassium iodide reaction wasobserved. The reaction mixture was cooled, evaporated and then tituratedwith hexane (500 ml). The precipitated succinimide was removed byfiltration and washed with additional hexane. Concentration afforded 101g of crude 3-chloro-5-methylbenzyl bromide.

EXAMPLE 10 3-Chloro-5-methylbenzyl alcohol

A solution of crude 3-chloro-5-methylbenzyl bromide (49.68 g) in 300 mlof glacial acetic acid containing 48.54 g of KOAc was heated at refluxfor 3 hours. The mixture was concentrated and then partitioned betweenwater (600 ml) and ether (500 ml). After repeated extractions withether, the combined organic layers were washed with saturated NaHCO₃solution (300 ml) and water (300 ml). After treatment with MgSO₄, theethereal solution was concentrated to give an oil, 41.5 g.

The crude acetate was dissolved in 200 ml of methanol and treated slowlywith a methanolic KOH solution (33.4 g in 100 ml). The reaction mixturewas stirred for 35 minutes at room temperature. The reaction mixture wasneutralized with acetic acid and concentrated under reduced pressure.The residue was partitioned between water (300 ml) and ether (200 ml).Concentration afforded 27.9 g of crude product which was purified bysilica gel chromatography (Eluant 95:5 CH₂ Cl₂ /Et₂ O) to give 15.6 g of3-chloro-5-methylbenzyl alcohol, m.p. 32°-34.5° C.

EXAMPLE 11 3-Chloro-5-methylbenzaldehyde

To a cold solution (-60° C.) of oxalyl chloride (14.88 ml) in 300 ml ofCH₂ Cl₂, dimethylsulfoxide (25.16 ml) in 75 ml of CH₂ Cl₂ was addedfollowed by the addition of 3-chloro-5-methylbenzyl alcohol (23 g) in100 ml of CH₂ Cl₂. To this cold mixture, triethylamine (103 ml) wasslowly added (exothermic) over 20 minutes. The reaction mixture was thenpermitted to warm to room temperature over 1.5 hours. The mixture wasthen added to 1 L of water and the layers separated. The CH₂ Cl₂ layerwas repeatedly washed with water and then dried with MgSO₄.Concentration afforded 25.4 g of an oil which was chromatographed onsilica gel. Elution with 60:40 hexane:CH₂ Cl₂ gave 20.01 g of pure3-chloro-5-methylbenzaldehyde.

EXAMPLE 12 3-Chloro-5-methylphenyl-(trichloromethyl)carbinol

A cold solution (-10° C.) of 3-chloro-5-methylbenzaldehyde (19.5 g) andchloroform (15.6 ml) in 76 ml of DMF was treated dropwise with a 5Mmethanolic KOH solution (17.16 ml). The reaction mixture was stirred for2 hours at -10° C. and then poured into a cold mixture of 170 ml of 1NHCl and 170 ml of CH₂ Cl₂ with vigorous stirring. The layers wereseparated and the aqueous phase further extracted with CH₂ Cl₂ (2×200ml). The combined organic layers were washed with water (3×100 ml) andthen dried over MgSO₄. Concentration produced 38.17 g of a crude oil.Purification by silica gel chromatography with 50:50 hexane:CH₂ Cl₂ aseluent gave 32.3 g of pure trichloromethyl carbinol.

EXAMPLE 13 3-Chloro-5-(trichlorovinyl)toluene

To a suspension of PCl₃ (13.75 g) in 275 ml of CH₂ Cl₂, a solution of(3-chloro-5-methylphenyl)-(trichloromethyl)-carbinol (17.87 g) in 125 mlof CH₂ Cl₂ was added dropwise. The reaction mixture was stirred for 30minutes prior to the addition of an additional 8 g of PCl₅. The reactionmixture was stirred for a total of 3 hours at ambient temperature priorto aqueous work-up which afforded 19.35 g of pentachloro product.

A solution of the pentachloro adduct (3.62 g) in 26 ml of methanol wasadded dropwise to a solution of NaOH (554 mg) in methanol (17 ml) over15 minutes. The reaction mixture was stirred at room temperature for anadditional 15 hours at which point HCl was added to adjust the pH of themixture to about 3. The solution was concentrated and then partitionedbetween water and ether. Repeated extractions with ether afforded 3.36 gof oil upon evaporation. This material was chromatographed on silica gel(hexane as eluent) to give 2.93 g of 3-chloro-5-(trichlorovinyl)toluene.

EXAMPLE 14 3-Chloro-5-(trichlorovinyl)benzyl bromide

A solution of 3-chloro-5-(trichlorovinyl)toluene (7.56 g) and dibenzoylperoxide (0.5 g) in 250 ml of benzene was heated at reflux.N-Bromosuccinimide (6.04 g) was added in portions and the reactionmixture stirred at reflux for 3 hours. The mixture was then evaporatedand the residue titurated with hexane (200 ml). The precipitatedsuccinimide was removed by filtration and washed with hexane (2×25 ml).The hexane was concentrated and the residual oil (10.1 g)chromatographed on silica with petroleum ether as eluant. The columnafforded 1.39 g of starting toluene, 1.18 g of dibromide, and 6.57 g ofthe desired benzyl bromide.

EXAMPLE 15 3-Chloro-5-(trichlorovinyl)benzyl azide

A solution of 3-chloro-5-(trichlorovinyl)benzyl bromide (3.57 g) andsodium azide (813 mg) in 50 ml of ethanol was heated at reflux for 30minutes. The reaction was then concentrated and the residuechromatographed on silica gel with petroleum ether as eluant to afford2.24 g of pure 3-chloro-5-(trichlorovinyl)benzyl azide.

EXAMPLE 165-Amino-1-[3-chloro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

Method A

A solution of cyanoacetamide (412 mg) in dimethyl formamide (DMF) (10ml) and hexane (2 ml) was treated with NaH (50% dispersion, 470 mg) atambient temperatures for 25 minutes. The solution was then filteredthrough celite and rinsed with DMF (2×2 ml). The filtrate was thencooled to 0° C. To this cold solution a solution of3-chloro-5-(trichlorovinyl)benzyl azide (980 mg) in 18 ml of DMF wasadded dropwise over 10 minutes. The resulting mixture was stirred for 45minutes at 0° C. and then poured into 50 ml of water containing 5 ml ofglacial acetic acid. The precipitate was collected and washed repeatedlywith water and with hexane. The solid was recrystallized from ethanol(11 ml) to give 345 mg of pure product, m.p. 191°-193.5° C.

Method B

A solution of 5-amino-1,2,3-triazole-4-carboxamide (386 mg) in 12 ml ofdry dimethylformamide (DMF) was treated with sodium hydride (50%dispersion in mineral oil, 154 mg). The reaction mixture was stirred atambient temperature for 20 minutes at which point a solution of3-chloro-5-(trichlorovinyl)benzyl bromide (1.01 g) in 6 ml of DMF wasadded dropwise. The resulting mixture was stirred for 1 hour at roomtemperature and then poured into 5 ml of water. Acetic acid was added toadjust the pH to 6.0. The aqueous mixture was then extracted withmethylene chloride (2×75 ml). The organic layers were back-washed withwater, dried with anhydrous magnesium sulfate and then concentratedunder vacuum. The residue was chromatographed on silica gel (97:3methylene chloride:methanol) to give:4-amino-1-[3-chloro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-5-carboxamide(497 mg) and5-amino-1-[3-chloro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide(346 mg).

EXAMPLE 17 4-Chloro-3-(trichlorovinyl)toluene

A cold (-10° C.) solution of 2-chloro-5-methylbenzaldehyde (20.8 g) andchloroform (16.6 ml) in 81 ml of dimethylformamide (DMF) is treateddropwise with a methanolic KOH solution (6.08 g in 18.3 ml). Thereaction mixture is stirred for 2 hours at -10° C. and then poured intoa mixture of 1N HCl (185 ml) and 185 ml of CH₂ Cl₂. The layers areseparated and the aqueous layer further extracted with CH₂ Cl₂ (2×75ml). The combined organic layers are washed with water (3x), dried withanhydrous magnesium sulfate and concentrated under reduced pressure. Theresidue (40 g) was chromatographed on silica with 1:1 hexane/CH₂ Cl₂ togive 24.49 g of trichloromethyl carbinol.

To a suspension of PCl₅ (12.4 g) in 250 ml of CH₂ Cl₂, a solution of thetrichloromethyl carbinol (24.49 g) in 100 ml of CH₂ Cl₂ was addeddropwise. The reaction mixture was stirred for 15 minutes at which pointan additional 7.5 g of PCl₃ was added. The reaction mixture was stirredfor an additional hour at room temperature and then carefully pouredinto 500 ml of ice-water. The layers were separated and the organiclayer was washed with water, saturated NaHCO₃ solution, and water again.Evaporation afforded 25 g of an oil which was chromatographed on silica(petroleum ether) to give 18.6 g of the pentachloride adduct.

This pentachloride adduct (17.6 g) was added to a solution of 3.1 g ofNaOH in 150 ml of methanol and the resulting mixture stirred for 16.5hours at room temperature. The reaction mixture was neutralized with HCl(pH 6) and then concentrated under reduced pressure. The residue waspartitioned between ether (400 ml) and water (100 ml). The layers wereseparated and the organic layer further washed with water and then driedwith anhydrous magnesium sulfate. Concentration gave an oil which wasdistilled at 93°-95°/3 mm to give pure4-chloro-3-(trichlorovinyl)toluene, 14.0 g.

EXAMPLE 18 4-Chloro-3-(trichlorovinyl)benzyl bromide

A solution of 4-chloro-3-(trichlorovinyl)toluene (13.77 g) and dibenzoylperoxide (1.0 g) in 500 ml of benzene was heated at reflux.N-Bromosuccinimide (11.6 g) was added in portions and the resultingmixture stirred at reflux for 1.5 hours (negative KI test). The reactionmixture was concentrated under reduced pressure. The residue waspartially dissolved in 300 ml of petroleum ether and the insolublesuccinimide removed by filtration. The filtrate was concentrated to give17.9 g of the benzyl bromide.

EXAMPLE 195-Amino-1-[4-chloro-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

A solution of 5-amino-1,2,3-triazole-4-carboxamide (1.65 g) in 50 ml ofdry dimethylformamide (DMF) was treated with sodium hydride (50% inmineral oil, 658 mg) and heated to 40° C. for 20 minutes. To thismixture a solution of 4-chloro-3-(trichlorovinyl)benzyl bromide (4.4 g)in 10 ml of DMF was added and heating was continued at 40° C. for 1hour. The reaction mixture was slowly added to 250 ml of water and thepH of the resulting solution adjusted with acetic acid to neutrality.The aqueous mixture was extracted with methylene chloride. The organiclayers were then back-washed with water (4X's), dried with magnesiumsulfate and concentrated. The residue was chromatographed on silica gel(97:3 CH₂ Cl₂ :CH₃ OH) to give:4-amino-1-[4-chloro-3-(trichlorovinyl)benzyl]-1,2,3-triazole-5-carboxamide(963 mg) and5-amino-1-[4-chloro-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide(650 mg), m.p. 174°-175° C.

EXAMPLE 20 3-Methyl-5-nitrobenzyl alcohol

A solution of 5-nitro-m-xylene (100 g) and dibenzyl peroxide (5.0 g) in1.35 L of benzene was heated at reflux. In portions N-bromosuccinimide(128 g) is added over 15 minutes. The reaction mixture is heated for anadditional hour at which point the mixture gave a negative KI test. Thereaction mixture was evaporated and the residue treated with 1 L ofhexane. The precipitated succinimide was removed by filtration. Thefiltrate was concentrated to give 174 g of a yellowish oil.

The crude benzylic bromide was dissolved in acetic acid (450 ml) towhich was added 100 g of potassium acetate. The resulting solution washeated at reflux for 1 hour and then concentrated. The residue waspartitioned between water (1 L) and ether (2×500 ml). The layers wereseparated and the combined organic layers were washed with saturatedNaHCO₃ and brine. Concentration afforded 142.7 g of crude benzylicacetate.

The crude benzylic acetate product was dissolved in 250 ml of methanoland treated with 75 ml of a 5N methanolic KOH solution. After 30 minutesthe reaction mixture was neutralized with acetic acid and concentrated.The residue was partitioned between water (500 ml) and ether (500 ml).The ethereal layer was washed with brine, dried with magnesium sulfate,and concentrated to give 131.5 g. The crude product was chromatographedon silica gel with methylene chloride to give 60.69 g of3-methyl-5-nitrobenzyl alcohol, m.p. 56.8°-57.9° C.

EXAMPLE 21 3-Methyl-5-nitrobenzaldehyde

To a cold (-60° C.) solution of oxalyl chloride (7.08 ml) in 177 ml ofCH₂ Cl₂, dimethylsulfoxide (12 ml) in 35 ml of CH₂ Cl₂ was added slowlyfollowed by the addition of 3-methyl-5-nitro benzaldehyde (11.84 g) in50 ml of CH₂ Cl₂. To this cold mixture, triethylamine (50 ml) was slowlyadded. The reaction mixture was then permitted to come to roomtemperature over the next hour. The reaction mixture was poured into 500ml of water and the layers separated. The organic layer was repeatedlywashed with water and dried over anhydrous magnesium sulfate.Concentration afforded an oil (12.1 g) which was used in the nextreaction without further purification.

EXAMPLE 22 3-(Trichlorovinyl)-5-nitrotoluene

A cold solution (-10° C.) of 3-methyl-5-nitrobenzaldehyde (60.6 g) andchloroform (45.4 ml) in 220 ml of dimethylformamide (DMF) was treateddropwise with a 5N methanolic solution of KOH (49.73 ml). The reactionmixture was stirred at -10° C. for 2 hours and then poured into a coldmixture of CH₂ Cl₂ (500 ml) and 1N HCl (500 ml) with vigorous stirring.The layers were then separated. The aqueous layer was further extractedwith CH₂ Cl₂ (1×500 ml). The combined organic layers were repeatedlywashed with water, dried over magnesium sulfate and concentrated underreduced pressure. The residue was chromatographed on silica gel (80:20CH₂ Cl₂ :hexane) to give 73 g of the trichloromethyl carbinolderivative.

To a suspension of PCl₅ (28.8 g) in 700 ml of CH₂ Cl₂, a solution of59.47 g of the trichloromethyl carbinol derivative in 300 ml of CH₂ Cl₂was added dropwise. After stirring the reaction mixture for 15 minutes,an additional 14.5 g of PCl₅ was added and the reaction mixture stirredovernight. The mixture was then poured slowly into 2 L of ice/water andthe layers separated. The organic layer was washed with saturatedNaHCO₃, water and then dried over magnesium sulfate. Concentration gave61.52 g of the tetrachloro derivative.

A solution of 61.0 g of this tetrachloro derivative in 420 ml ofmethanol was added dropwise to a solution of NaOH (10.96 g) in 463 ml ofmethanol. The reaction mixture was stirred overnight at roomtemperature. The pH of the mixture was then adjusted to near 6 withglacial acetic acid. The reaction mixture was concentrated and theresulting residue partitioned between ether (800 ml) and water (500 ml).The layers were separated and the aqueous layer further extracted with500 ml of ether. The combined organic layers were washed with water(3×300 ml) and then dried over magnesium sulfate. Concentration afforded53.23 g of 3-(trichlorovinyl)-5-nitrotoluene.

EXAMPLE 23 3-Methyl-5-(trichlorovinyl)Aniline

To a warm solution of 3-(trichlorovinyl)-5-nitrotoluene (10.95 g) in 150ml of ethanol, an aqueous solution of ammonium sulfide (30 ml of acommercial 46-52% aqueous solution diluted to 90 ml with water) wasadded in one portion. The resulting heterogeneous solution was heated ina 100° C. oil bath for 30 minutes. The hot reaction mixture was filteredand the precipitate thoroughly washed with ethanol. The filtrate wasdiluted with 1.2 L of brine and then extracted with methylene chloride(2×400 ml). The combined organic layers were washed with brine and driedover anhydrous magnesium sulfate. Concentration afforded 9.36 g of anoil.

EXAMPLE 24 3-Methyl-5-(trichlorovinyl)benzenediazoniumhexafluorophosphate

3-Methyl-5-(trichlorovinyl)aniline (9.9 g) was mixed with 32 ml ofconcentrated HCl and 75 ml of water. The resulting suspension was cooledto -10° C. and a solution of sodium nitrite (3.5 g in 7 ml H₂ O) wasadded dropwise. The reaction mixture was stirred at -10° C. for 10minutes and then at 0° C. for 30 minutes. The cold (-10° C.) solutionwas filtered and the filtrate treated with 10 ml of a 60% solution ofHPF₆. The mixture was shaken (0° C.) for 20 minutes and then filtered.The collected salt was washed with cold water repeatedly and dried in avacuum oven at room temperature over P₂ O₅ to give 11.30 g of thedesired hexafluorophosphate salt.

EXAMPLE 25 3-Bromo-5-(trichlorovinyl)toluene

To a suspension of CuBr₂ (14.1 g) in dimethylsulfoxide (DMSO), asolution of 3-methyl-5-(trichlorovinyl)benzenediazoniumhexafluorophosphate (11.3 g) in 35 ml of DMSO was added. The reactionmixture was stirred at 25° C. for 15 minutes and then at 35° C. for 10minutes. The reaction mixture was cooled (0° C.) and then diluted with500 ml of ice water. The aqueous solution was extracted with ether(3×150 ml). The combined ethereal layers were washed with brine (2×100ml), dried with magnesium sulfate and concentrated to give 7.77 g of anoil. Chromatography on silica gel (Hexane) afforded 6.88 g of pureproduct.

EXAMPLE 26 3-Bromo-5-(trichlorovinyl)benzyl bromide

A solution of 3-bromo-5-(trichlorovinyl)toluene (1.76 g) and 100 mg ofdibenzoyl peroxide in 100 ml of benzene was heated at reflux.N-bromosuccinimide (1.3 g) was added in portions and the reactionmixture stirred at reflux for 5.5 hours. The reaction mixture wasconcentrated and the residue triturated with 100 ml of hexane. Theprecipitated succinimide was collected by filtration and thoroughlywashed with hexane. The filtrate was concentrated under reduced pressureto give 2.2 g of a crude mixture containing the desired benzyl bromide.

EXAMPLE 27 3-Bromo-5-(trichlorovinyl)benzyl azide

A solution of crude 3-bromo-5-(trichlorovinyl)benzyl bromide (2.2 g) andsodium azide (760 mg) in 30 ml of ethanol was heated at reflux for 1hour. The reaction solution was concentrated under reduced pressure andthe residue triturated with 100 ml of hexane. The mixture was filteredand the filtrate chromatographed on silica (hexane) to give 1.1 g ofpure azide.

EXAMPLE 285-Amino-1-[3-bromo-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

To a hot (60° C.) solution of cyanoacetamide (546 mg) in 20 ml ofethanol, 6.47 ml of a methanolic solution of NaOH (1N) was added and theresulting mixture was stirred at 60° C. for 20 minutes. A solution of3-bromo-5-(trichlorovinyl)benzyl azide (1.02 g) in 10 ml of ethanol wasadded and the reaction mixture heated at 60° C. for two hours. The pH ofthe solution was adjusted to ˜6 with acetic acid and then concentratedto a small volume. Dilution with 50 ml of water afforded a precipitatewhich was washed thoroughly with water. The precipitate wasrecrystallized from 8 ml of ethanol to give 466 mg of pure product, m.p.175°-177° C.

EXAMPLE 29 2-(Trichlorovinyl)-p-xylene

A cold (-10° C.) solution of 2,5-dimethylbenzaldehyde (44.25 g) andchloroform (150.2 g) in 531 ml of dimethylformamide (DMF) was treateddropwise with a methanolic KOH solution (39.7 g of KOH in 119 ml ofmethanol). The reaction mixture was stirred for 2 hours at -8° C. atwhich point the reaction mixture was poured onto a cold mixture of 450ml of benzene and 450 ml of a 1N HCl solution, the reaction mixturepermitted to come to room temperature. The layers were then separatedand the organic layer was further washed with water. Concentration underreduced pressure afforded 90.98 g of crude trichlorovinyl carbinol.

To a suspension of PCl₃ (75 g) in 1.5 L of CH₂ Cl₂, a solution of thecrude trichlorovinyl carbinol (90.98 g) in 400 ml of CH₂ Cl₂ was addeddropwise. The reaction mixture was stirred for 30 minutes at which pointadditional PCl₅ (45 g) was added. The reaction mixture was stirred for 3hours and then subjected to aqueous work-up which afforded 88.8 g ofcrude tetrachloro derivative.

A solution of this tetrachloro adduct (83.8 g) in 375 ml of methanol wasadded dropwise to a solution of NaOH (14.8 g) in methanol (750 ml). Theresulting solution was stirred at ambient temperature for 29 hours. Thereaction mixture was concentrated and then partitioned between ether andwater. The ethereal fraction was dried with anhydrous magnesium sulfate,evaporated and chromatographed on silica gel. Elution with hexane gave41.5 g of pure 2-(trichlorovinyl)-p-xylene.

EXAMPLE 30 4-Methyl-3-(trichlorovinyl)benzyl bromide

To a hot solution of 2-(trichlorovinyl)-p-xylene (25.4 g) and dibenzoylperoxide (3.2 g) in 1000 ml of benzene, N-bromosuccinimide (20.79 g) wasadded in portions. The resulting mixture was heated at reflux for 15minutes at which point no N-bromosuccinimide was evident. The reactionsolution was evaporated and the residual oil suspended in 90:10petroleum ether:methylene chloride (250 ml). The precipitatedsuccinimide was collected by filtration and thoroughly washed with theabove solvent system. The filtrate was concentrated and thenchromatographed on silica gel. Elution with 90:10 petroleumether:methylene chloride gave 20.9 g of a mixture containing4-methyl-3-(trichlorovinyl)benzyl bromide and4-methyl-2-(trichlorovinyl)benzyl bromide.

EXAMPLE 31 4-Methyl-3-(rrichlorovinyl)benzyl alcohol

A solution of the crude mixture of benzyl bromides[4-methyl-3-(trichlorovinyl)benzyl bromide and4-methyl-2-(trichlorovinyl)benzyl bromide, 29.32 g] in 700 ml of drytetrahydrofuran was treated with 33.92 g of tetra-n-butyl ammoniumacetate and stirred at room temperature for 1 hour. The reaction mixturewas concentrated under reduced pressure and the residual oil trituratedwith 400 ml of hexane. The precipitate was removed by filtration andthoroughly washed with hexane (2×200 ml). Concentration gave 28.2 g of ayellow oil which was dissolved in 266 ml of methanol and treateddropwise with an aqueous 1N KOH solution (55 ml). The reaction mixturewas stirred at ambient temperature for 30 minutes and then partiallyconcentrated. The concentrate was then extracted with ether (1000 ml).The ethereal layer was back-washed with brine (2×200 ml), dried withanhydrous magnesium sulfate, and concentrated in vacuum to give 28.2 gof an oil. Chromatography on silica (90:10 methylene chloride:ether)gave 8.92 g of 4-methyl-2-(trichlorovinyl)benzyl alcohol and 10.67 g ofthe desired 4-methyl-3-(trichlorovinyl)benzylalcohol.

EXAMPLE 32 4-Methyl-3-(trichlorovinyl)benzyl chloride

A solution of 4-methyl-3-(trichlorovinyl)benzyl alcohol (2.06 g) andtriphenylphosphine (2.58 g) in 100 ml of carbon tetrachloride was heatedat reflux for 48 hours. The reaction mixture was concentrated underreduced pressure and the residue dissolved in CH₂ Cl₂ (200 ml). Thisorganic solution was shaken with 30% H₂ O₂ (10 ml) and then diluted withwater (100 ml) and the layers separated. The organic layer was furtherwashed with water, dried with anhydrous magnesium sulfate andconcentrated to give 4.37 g of crude product. Chromatography on silica(1:1 hexane:methylene chloride) gave 1.81 g of4-methyl-(trichlorovinyl)benzyl chloride.

EXAMPLE 33 4-Methyl-3-(trichlorovinyl)benzyl azide

A solution of 4-methyl-3-(trichlorovinyl)benzyl chloride (1.81 g) andsodium azide (650 mg) in 20 ml of ethanol was heated at reflux for 5hours. The reaction mixture was concentrated and then chromatographed onsilica gel. Elution with 1:1 hexane:methylene chloride afforded 1.65 gof pure azide.

EXAMPLE 345-Amino-1-[4-methyl-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

To a hot (60° C.) solution of cyanoacetamide (1.09 g) in 30 ml ofethanol, 13 ml of a methanolic solution of NaOH (1N) was added and theresulting mixture was stirred at 60° C. for 20 minutes. At this point asolution of 4-methyl-3-(trichlorovinyl)benzyl azide (1.65 g) in 10 ml ofethanol was added and the reaction mixture stirred at 60° C. for anadditional two hours. The precipitate was removed by filtration andrinsed with ethanol and ether. The filtrate was diluted with water (200ml) and the resulting precipitate collected (1.56 g). The crude productwas chromatographed on silica with 95:5 methylene chloride:methanol togive 889 mg of5-amino-1-[4-methyl-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide,m.p. 196°-197° C.

EXAMPLE 35 3-Methyl-5-(trichlorovinyl)benzyl bromide

To a refluxing solution of 5-(trichlorovinyl)-m-xylene (32.28 g) anddibenzoyl peroxide (3.43 g) in 1300 ml of benzene, N-bromosuccinimide(30.21 g) was added in portions. The resulting mixture was heated atreflux for 30 minutes at which point no N-bromosuccinimide was evident.The reaction mixture was concentrated under reduced pressure and theresidue triturated with 250 ml of hexane. The precipitated succinimidewas collected by filtration and thoroughly washed with hexane. Thefiltrate was concentrated and the residue chromatographed on silica(petroleum ether) to give 26.2 g of the desired benzyl bromide.

EXAMPLE 36 3-Methyl-5-(trichlorovinyl)benzyl azide

A solution of 3-methyl-5-(trichlorovinyl)benzyl bromide (3.14 g) andsodium azide (1.0 g) in 25 ml of ethanol was heated at reflux for 2hours. The reaction mixture was concentrated under reduced pressure andthe resulting oil triturated with 50 ml of hexane. The mixture wasfiltered and the filtrate concentrated to give 2.64 g of azide.

EXAMPLE 375-Amino-1-[3-methyl-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

To a hot (60° C.) solution of cyanoacetamide (1.8 g) in 57 ml ofethanol, 21.3 ml of a 1N methanolic solution of NaOH was added and theresulting mixture stirred for 20 minutes. A solution of3-methyl-5-(trichlorovinyl)benzyl azide (2.64 g) in 20 ml of ethanol wasadded and the reaction mixture stirred at 60° C. for an additional twohours. The pH of the solution was adjusted to 6 with acetic acid. Thesolution was diluted with water (300 ml) and the resulting precipitatecollected and rinsed thoroughly with water. The solid was thenchromatographed on silica gel (97:3) CH₂ Cl₂ :CH₃ OH) to give 980 mg ofpure triazole.

EXAMPLE 38 3-Methyl-5-(trichlorovinyl)benzyl alcohol

A suspension of potassium acetate (4.4 g) and3-methyl-5-(trichlorovinyl)benzyl bromide (7.2 g) in 50 ml of glacialacetic acid heated at reflux for two hours. The reaction mixture wasconcentrated and the residue partitioned between ether (150 ml) andwater (150 ml). The layers were separated and the aqueous phase furtherextracted with ether. The combined ethereal layers were washed withsaturated NaHCO₃ and water and then dried with anhydrous magnesiumsulfate. Concentration afforded the crude acetate which was dissolved in50 ml of methanol and treated with 4.5 g of KOH. The resulting mixturewas stirred at room temperature for 45 minutes. The pH of the solutionwas adjusted to @ 6 with acetic acid. The reaction mixture was thenconcentrated and the residue partitioned between ether (150 ml) andwater (150 ml). The layers were separated and the ethereal layerconcentrated to give 6.5 g of an oil which was chromatographed on silicagel (80:10:10 hexane:methylene chloride:ethyl acetate) to give 5.8 g ofpure alcohol, m.p. 63°-65.5° C.

EXAMPLE 39 3-Methyl-5-(trichlorovinyl)benzaldehyde

To a cold (-60° C.) solution of oxalyl chloride (3.17 ml) in 65 ml ofdry methylene chloride (CH₂ Cl₂), dimethyl sulfoxide (DMSO) (5.37 ml) in16 ml of CH₂ Cl₂ was added followed by the addition of 7.86 g of3-methyl-5-(trichlorovinyl)benzyl alcohol in 16 ml of CH₂ Cl₂, to thiscold mixture, triethylamine (22 ml) was slowly added. The reactionmixture was permitted to warm to room temperature over 1.5 hours. Thereaction mixture was then added to 200 ml of water and the layersseparated. The organic layer was repeatedly washed with water and thendried with magnesium sulfate. Concentration afforded 8.16 g of an oilwhich was chromatographed on silica gel (60:40 hexane:CH₂ Cl₂) to give7.82 g of pure aldehyde, m.p. 42°-43° C.

EXAMPLE 40 3,5-Di(trichlorovinyl)toluene A cold solution (31 10° C.) of3-methyl-5 -(trichlorovinyl)benzaldehyde (7.72 g) and chloroform (3.8ml) in 18.5 ml of dimethylformamide (DMF) was treated dropwise with a 5Nmethanolic solution of KOH (4.19 ml). The mixture was stirred at -10° C.for 2 hours and then poured into a cold mixture of 42 ml of 1N HCl and42 ml of CH₂ Cl₂ with vigorous stirring. The layers were separated andthe aqueous layer further extracted with CH₂ Cl₂. The combined organiclayers were washed with water and then dried with MgSO₄. Concentrationafforded 15.9 g of a yellow oil which was chromatographed on silica gel(70:30 CH₂ Cl₂ :hexane) to give 10.7 g of pure trichloromethyl carbinol.

A solution of this trichloromethyl carbinol (10.7 g) in 50 ml of CH₂ Cl₂was added dropwise to a suspension of PCl₅ (4.0 g) in 65 ml of CH₂ Cl₂.The reaction mixture was stirred for 30 minutes at which point anadditional 2.4 g of PCl₅ was added. The mixture was stirred at roomtemperature for 2 hours and then poured carefully into 250 ml ofice-water. The layers were separated and the aqueous layer furtherextracted with CH₂ Cl₂. The combined organic layers were washed withwater, saturated NaHCO₃ and brine. The organic solution was dried withMgSO₄ and concentrated to give 11.0 g of product. This material wasdissolved 30 ml of methanol and treated with a solution of NaOH (1.7 g)in 70 ml of methanol. The reaction mixture was stirred at roomtemperature for 16 hours and then the pH adjusted to 6 with acetic acid.The mixture was concentrated under reduced pressure and the residuepartitioned between ether (200 ml) and water (200 ml). The layers wereseparated and the aqueous phase further extracted with ether. Thecombined ethereal layers were washed with water and then dried withMgSO₄. Concentration afforded 9.63 g of 3,5-di(trichlorovinyl)toluene,m.p. 41.4°-44.6° C.

EXAMPLE 41 3,5-Di(trichlorovinyl)benzyl bromide

A solution of 3,5-di(trichlorovinyl)toluene (6.0 g) and dibenzoylperoxide (200 mg) in 150 ml of benzene was heated at reflux.N-Bromosuccinimide (3.6 g) was added in portions and the reactionmixture stirred at reflux for 3 hours. The mixture was evaporated andthe residue triturated with 200 ml of hexane. The precipitatedsuccinimide was collected and the filtrate concentrated to five 7.9 g ofcrude benzyl bromide.

EXAMPLE 42 3,5-Di(trichlorovinyl)benzyl azide

A solution of crude 3,5-di(trichlorovinyl)benzyl bromide (7.9 g) andsodium azide (1.9 g) in 200 ml of ethanol was heated at reflux for 1.5hours. The reaction mixture was concentrated and the residue partitionedbetween 100 ml of ether and 100 ml of water. The layers were separatedand the aqueous phase further extracted with ether. The ethereal layerswere washed with water, dried with MgSO₄, and concentrated to give 7.03g of an oil. This material was chromatographed on silica gel (hexanethen 90:10 hexane:CH₂ Cl₂) to give 3.52 g of pure azide.

EXAMPLE 435-Amino-1-[3,5-di(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

To a hot (60° C.) solution of cyanoacetamide (0.692 g) in 25 ml ofethanol, 8.2 ml of a 1N methanolic solution of NaOH was added and theresulting mixture stirred for 20 minutes. 3,5-Di(trichlorovinyl)benzylazide (1.5 g) was added in one portion and the resulting mixture stirredat 60° C. for 1 hour. The pH of the mixture was adjusted to 6 withacetic acid. The reaction mixture was then concentrated to a reducedvolume and diluted with 100 ml of water. The aqueous mixture wasextracted with CH₂ Cl₂ (3×100 ml). The combined organic layers werewashed with water, dried with MgSO₄ and concentrated to give 1.5 g ofcrude product. This material was chromatographed on silica gel (95:5 CH₂Cl₂ :CH₃ OH) to give 890 mg of a solid. Recrystallization from 5 ml ofethanol provided pure triazole, m.p. 167°-169° C.

EXAMPLE 44 3-Fluoro-5-(trichlorovinyl)toluene

A mechanically stirred mixture of3-methyl-5-(trichlorovinyl)benzenediazonium hexafluorophosphate (10g)and sea sand (90 g) are immersed in an oil bath at 160°-165° C. Themixture is stirred for 10 minutes at this elevated temperature and thenpermitted to cool. The reaction mixture is triturated in 300 ml of etherand filtered. The filtrate is washed with aqueous sodium bicarbonate andwater. The ether solution is dried with MgSO₄ and concentrated underreduced pressure. The residue is chromatographed on silica gel (hexane)to yield 3-fluoro-5-(trichlorovinyl))toluene.

EXAMPLE 45 3-Fluoro-5-(trichlorovinyl)benzyl bromide

To a solution of 3-fluoro-5-(trichlorovinyl)toluene (2.39 g) anddibenzoyl peroxide (0.2 g) in 60 ml of benzene at reflux,N-bromosuccinimide (2.21 g) is added in portions. The mixture is heatedat reflux until the solution gives a negative reaction with potassiumiodide. The reaction mixture is concentrated and the residue trituratedwith 100 ml of hexane. The precipitated succinimide is collected byfiltration and the filtrate concentrated and then chromatographed onsilica gel (hexane) to give the desired benzyl bromide.

EXAMPLE 46 3-Fluoro-5-(trichlorovinyl)benzyl azide

A solution of 3-fluoro-5-(trichlorovinyl)benzyl bromide (3.18 g) andsodium azide (0.975 g) in 25 ml of ethanol is heated at reflux for 2hours. The reaction mixture is concentrated and the residue trituratedwith 50 ml of hexane. The mixture is filtered and the filtrateconcentrated to give the desired azide.

EXAMPLE 475-Amino-1-[3-fluro-5-(trichlorovinyl)benzyl-1,2,3-triazole-4-carboxamide

To a hot (60° C.) solution of cyanoacetamide (3.0 g) in 120 ml ofethanol, 42.6 ml of a 1N methanolic solution of NaOH is added. Theresulting mixture is stirred for 20 minutes. A solution of3-fluoro-5-(trichlorovinyl)benzyl azide (5.2 g) in 40 ml of ethanol isadded and the reaction mixture stirred at 60° C. for an additional hour.The mixture is cooled and then treated with acetic acid to adjust the pHto 6. The solution is then concentrated under vacuum to a small volumeand diluted with water. The precipitate is collected by filtration andthoroughly washed with water. The solid is then chromatographed onsilica gel (97:3 CH₂ Cl₂ :CH₃ OH) to yield pure triazole.

EXAMPLE 48 3-Chloro-4-(trichlorovinyl)toluene

A cold (-10° C.) solution of 2-chloro-4-methylbenzaldehyde (15.96 g) andchloroform (18.6 g) in 62 ml of dimethylformamide (DMF) was treateddropwise with a methanolic solution of KOH (4.66 g in 14 ml). Thereaction mixture was stirred at -10° C. for two hours and then pouredinto a cold mixture of 1N HCl (140 ml) and CH₂ Cl₂ (140 ml) withvigorous stirring. The layers were separated and the aqueous layerfurther extracted with CH₂ Cl₂. The combined organic layers were washedwith water, dried with MgSO₄, and concentrated to give 15.1 g.Chromatography on silica gel (60:40 CH₂ Cl₂ :hexane) gave 12.88 g oftrichloromethyl carbinol product.

To a suspension of PCl₅ (6.52 g) in 150 ml of CH₂ Cl₂, a solution of thetrichloromethyl carbinol (12.88 g) in 75 ml of CH₂ Cl₂ was addeddropwise. The reaction mixture was stirred for 30 minutes and then anadditional 4.0 g of PCl₅ was added. The reaction mixture was stirred for3 hours and then carefully subjected to aqueous work-up to give 13.11 gof crude product. Chromatography on silica gel (petroleum ether)provided 11.7 g of pure pentachloro derivative.

A solution of this pentachloro derivative (11.68 g) in 50 ml of methanolwas added dropwise to a solution of NaOH (2.06 g) in methanol (100 ml).The reaction mixture was stirred at room temperature for 18 hours atwhich point the pH of the solution was adjusted to 6 with HCl. Thereaction mixture was concentrated and then partitioned between ether(400 ml) and water (200 ml). The ethereal layer was dried with MgSO₄ andconcentrated to give 10.1 g of 3-chloro-4-(trichlorovinyl)toluene.

EXAMPLE 49 3-Chloro-4-(trichlorovinyl)benzyl bromide

To a solution of 3-chloro-4-(trichlorovinyl)toluene (10.1 g) anddibenzoyl peroxide (726 mg) in 360 ml of benzene at reflux,N-bromosuccinimide (8.42 g) was added in portions. The mixture washeated at reflux for 2 hours at which point the mixture gave a negativeKI response. The reaction mixture was concentrated and the residuetriturated with 300 ml of petroleum ether. The mixture was filtered andthe filtrate concentrated in vacuo to give 14.77 g of crude benzylbromide.

EXAMPLE 505-Amino-1-[3-chloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

A solution of 5-amino-1,2,3-triazole-4-carboxamide (1.65 g) in 50 ml ofdimethylformamide (DMF) was treated with NaH (50% in mineral oil, 658mg) and stirred at room temperature for 20 minutes. To this mixture asolution of 3-chloro-4-(trichlorovinyl)benzyl bromide (5.7 g) in 10 mlof DMF was added and the resulting reaction mixture stirred for 1 hour.The mixture was carefully poured into 500 ml of water and the pH of theresulting solution adjusted to 6 with acetic acid. The mixture was thenextracted with CH₂ Cl₂ (2×400 ml). The organic layers were dried andconcentrated. The resulting residue was chromatographed on silica gel(97:3 CH₂ Cl₂ :CH₃ OH) to give:4-amino-1-[3-chloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-5-carboxamide(2.28 g) and5-amino-1-[3-chloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide(1.2 g). This latter material was recrystallized from ethanol to givepure triazole, m.p. 185°-186.5° C.

EXAMPLE 51 3-(Trichlorovinyl)toluene

From the reaction of m-tolualdehyde (18.52 g) and chloroform (27.88 ml)in dimethylformamide (93 ml) with KOH (7.0 g) in methanol (21 ml) as inExample 29, 39.4 g of crude trichloromethyl carbinol was obtained. Asuspension of PCl₅ (21.2 g) in 500 ml of CH₂ Cl₂ was treated with thecrude trichloromethyl carbinol as in Example 29. After 15 minutes atroom temperature, an additional portion of PCl₅ (12.91 g) was added.Appropriate work-up yielded 39.2 g of crude tetrachloro derivative.

A solution of this tetrachloro derivative (39.2 g) in methanol wasslowly added to a solution of NaOH (7.66 g) in methanol (370 ml) andstirred at room temperature for 24 hours. The reaction mixture wasacidified to pH 6 with acetic acid and partially evaporated in vacuo.The oily residue was partitioned between ether (250 ml) and water (200ml). The aqueous layer was further extracted with ether (200 ml). Thecombined extracts were washed with water and dried over MgSO₄.Concentration afforded the crude product which was purified bychromatography on silica gel (petroleum ether) to give 26.47 g of3-(trichlorovinyl)toluene.

EXAMPLE 52 3-(Trichlorovinyl)benzyl azide

From the reaction of 3-(trichlorovinyl)toluene (4.35 g), dibenzoylperoxide (0.363 g), and N-bromosuccinimide (4.21 g) in 180 ml of benzeneas in Example 30, 6.56 g of crude benzyl bromide was obtained.

The reaction of this crude benzyl bromide (6.56 g) and sodium azide(1.92 g) in ethanol (90 ml) as in Example 33 gave 5.48 g of crude benzylazide. Chromatography on silica gel yielded 3.29 g of pure3-(trichlorovinyl)benzyl azide.

EXAMPLE 535-Amino-1-[3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

From the reaction of cyanoacetamide (1.84 g), 3-(trichlorovinyl)benzylazide (2.59 g) and 1N methanolic NaOH (22.2 ml) in ethanol (60 ml) as inExample 34, 2.03 g of crude triazole was obtained. Afterrecrystallization from isopropanol, 1.35 g of pure5-amino-1-[3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide, m.p.186°-188° C., was obtained.

EXAMPLE 54 4-(Trichlorovinyl)toluene

From the reaction of p-tolualdehyde (18.52 g) and chloroform (27.88 g)in dimethylformamide (93 ml) with KOH (7.0 g) in methanol (21 ml) as inExample 29, 39.4 g of crude trichloromethyl carbinol was obtained.

A suspension of PCl₅ (21.2 g) in 500 ml of CH₂ Cl₂ was treated with asolution of the crude carbinol (39.4 g) in 120 ml of CH₂ Cl₂ as inExample 29. After 15 minutes at room temperature an additional portionof PCl₅ (12.91 g) was added. The same reaction conditions and work-up asin Example 29 yielded 41.7 g of crude tetrachloro derivative.

A solution of the tetrachloro adduct in methanol (100 ml) was slowlyadded to a solution of sodium hydroxide (7.66 g) in methanol (370 ml)and stirred at room temperature for 18 hours. The reaction mixture wasacidified to pH 6 with acetic acid and partially evaporated in vacuo.The oily residue was partitioned between ether (250 ml) and water (200ml). The aqueous layer was further extracted with an additional 200 mlof ether. The combined extracts were washed with water, dried withMgSO₄, and concentrated to yield the crude product. Purification onsilica gel (petroleum ether) yielded 14.69 g of pure4-(trichlorovinyl)toluene.

EXAMPLE 55 4-(Trichlorovinyl)benzyl azide

From the reaction of 4-(trichlorovinyl)toluene (4.35 g), dibenzoylperoxide (0.363 g), and N-bromosuccinimide (4.21 g) in 180 ml of benzeneat reflux as in Example 30, 6.7 g of crude benzyl bromide was obtained.

The reaction of this crude benzyl bromide (6.7 g) and sodium azide (1.92g) in ethanol (90 ml) at reflux as in Example 33 yielded 5.7 g of crudebenzyl azide. Chromatography on silica gel afforded 3.98 g of pure4-(trichlorovinyl)benzyl azide.

EXAMPLE 565-Amino-1-[4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

From the reaction of cyanoacetamide (1.84 g), 4-(trichlorovinyl)benzylazide (2.59 g), and 1N NaOH (22.2 ml) in ethanol (60 ml) as in Example34, 2.00 g of crude triazole was obtained. Recrystallization fromisopropanol gave 0.867 g of pure5-amino-1-[4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide, m.p.200°-203° C.

EXAMPLE 57 3,5-Dichloro-4-(trichlorovinyl)toluene

2,6-Dichloro-4-methylaniline (30.4 g) was converted to2,6-dichloro-4-methylbenzaldehyde (6.54 g) according to the generalprocedure of Jolad and Rajagopal (Organic Synthesis, Collected Volume I,pp 139-141). This aldehyde (2.44 g) was reacted with chloroform (2.40 g)and methanolic KOH (610 mg in 1.8 ml) in dimethylformamide (8 ml)according to the procedure described in Example 29 to give 3.5 g ofcrude trichloromethyl carbinol.

A suspension of PCl₅ (2.80 g) in 60 ml of CH₂ Cl₂ was treated with asolution of the crude trichloromethyl carbinol (3.5 g) in 20 ml of CH₂Cl₂ as in Example 29. After 15 minutes at room temperature, anadditional 1.6 g of PCl₅ was added. Appropriate reaction times andwork-up as in Example 29 afforded 2.8 g of hexachloro product. Asolution of this material (2.8 g) in 15 ml of methanol is added dropwiseto a solution of NaOH (0.5 g) in 25 ml of methanol as in Example 29. Thereaction mixture is stirred at room temperature for 15 hours at whichpoint the pH of the solution is adjusted to 6 with hydrochloric acid.The reaction mixture is concentrated and partitioned between ether andwater. The ethereal layer is dried and concentrated. The residue ischromatographed on silica gel to give pure3,5-dichloro-4-(trichlorovinyl)toluene.

EXAMPLE 58 3,5-Dichloro-4-(trichlorovinyl)benzyl azide

From the reaction of 3,5-dichloro-4-(trichlorovinyl)toluene (2.15 g),dibenzoyl peroxide (0.33 g), and N-bromosuccinimide (2.05 g) in 85 ml ofbenzene at reflux as in Example 30,3,5-dichloro-4-(trichlorovinyl)benzyl bromide is obtained. This material(2.7 g) and sodium azide (0.8 g) in ethanol (25 ml) is heated for 2hours. The crude product is chromatographed on silica gel to give pure3,5-dichloro-4-(trichlorovinyl)benzyl azide.

EXAMPLE 595-Amino-1-[3,5-dichloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

From the reaction of cyanoacetamide (0.92 g),3,5-dichloro-4-(trichlorovinyl)benzyl azide (1.25 g), and 1N methanolicNaOH (11.1 ml) in ethanol (30 ml) as in Example 34, crude triazole isobtained. This material is chromatographed on silica gel to give pure5-amino-1-[3,5-dichloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.

EXAMPLE 60 5-(Trifluoromethyl)-m-xylene

A solution of 5-iodo-m-xylene (2.3 g) in dimethylformamide (DMF) (30 ml)and copper bronze (0.65 g) in a stainless steel tube is cooled andtreated with trifluoromethyliodide (15 g). The tube is sealed and heatedat 130°-140° C. in a rocking autoclave for 6 hours. After cooling andventing, the reaction mixture is diluted with water and extracted withn-hexane (2×200 ml). The combined hexane extracts are washed withaqueous NaHCO₃ and water. After drying over MgSO₄, the solvent isremoved under reduced pressure. The residue is subjected tochromatography over silica gel to yield purified5-(trifluoromethyl)-m-xylene.

EXAMPLE 61 3-Trifluoromethyl-5-methylbenzyl bromide

A solution of 5-trifluoromethyl-m-xylene (3.4 g) and dibenzoyl peroxide(0.25 g) in 100 ml of benzene at reflux is treated withN-bromosuccinimide (4.4 g) in portions. The mixture is heated until anegative potassium iodide test is obtained. The reaction mixture iscooled and concentrated in vacuo. The residue is triturated withn-hexane and the solids are removed by filtration. The filtrate isevaporated to give the oily crude benzyl bromide.

EXAMPLE 62 3-Trifluoromethyl-5-methylbenzyl alcohol

The crude benzyl bromide (5.3 g) is dissolved in acetic acid (50 ml) andtreated with potassium acetate (2.9 g). The mixture is heated at refluxfor 2 hours. The solvent is removed and the residue extracted withether. The ether extracts are washed with aqueous NaHCO₃ and water.After drying with MgSO₄, the ethereal solution is evaporated to yieldthe crude benzyl acetate which is then hydrolyzed to the benzyl alcoholwith methanolic KOH as in Example 10. The crude product is thenchromatographed on silica gel to give 3-trifluoromethyl-5-methylbenzylalcohol.

EXAMPLE 63 3-Trifluoromethyl-5-methylbenzaldehyde

A solution of oxalyl chloride (2.8 ml) in 20 ml of CH₂ Cl₂ is treatedwith a solution of dimethyl sulfoxide (DMSO) (5.0 ml) in 15 ml of CH₂Cl₂ at -60° C. as in Example 11. To this mixture is added the3-trifluoromethyl-5-methylbenzyl alcohol (5.4 g) in CH₂ Cl₂ (20 ml)followed by 20 ml of triethlyamine. Appropriate reaction conditions andwork-up as in Example 11 afforded3-trifluoromethyl-5-methylbenzaldehyde.

EXAMPLE 64 3-Trifluoromethyl-5-trichlorovinyltoluene

The reaction of 3-trifluoromethyl-5-methylbenzaldehyde (5.8 g) andchloroform (3.8 ml) in DMF (20 ml) with 5N methanolic KOH (4.19 ml) asin Example 29 yields the crude trichloromethyl carbinol. This materialas a solution in CH₂ Cl₂ (50 ml) is added to a stirred suspension ofPCl₅ (4.0 g) in 65 ml of CH₂ Cl₂ at room temperature. After 15 minutesan additional portion of PCl₅ (2.4 g) is added. The reaction conditionand work-up is the same as in Example 29. This crude tetrachloroderivative is dissolved in 50 ml of methanol and treated with a solutionof NaOH (2.2 g) in methanol (30 ml). The reaction mixture is stirred for16 hours and then treated with acetic acid to adjust the pH of themixture to 6. The reaction mixture is concentrated and the residuepartitioned between ether and water. The layers are separated and theaqueous phase repeatedly extracted with ether. The combined organiclayers are washed with brine, dried with MgSO₄, and concentrated underreduced pressure. The crude product is chromatographed on silica gel toyield pure 3-trifluoromethyl-5-trichlorovinyltoluene.

EXAMPLE 65 3-Trifluoromethyl-5-trichlorovinylbenzyl azide

A solution of 3-trifluoromethyl-5-trichlorovinyltoluene (2.89 g) anddibenzoyl peroxide (0.2 g) in benzene (40 ml) at reflux is treated withN-bromosuccinimide (2.21 g) as in Example 30. The hexane soluble portionaffords the crude benzyl bromide (3.67 g) which when heated with sodiumazide (0.975 g) in ethanol (30 ml) at reflux for 2 hours as in Example33 provides the desired benzyl azide.

EXAMPLE 665-Amino-1-[3-(trifluoromethyl)-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide

From the reaction of 3-trifluoromethyl-5-trichlorovinylbenzyl azide(1.07 g) and cyanoacetamide (0.616 g) in 20 ml of ethanol with 1Nmethanolic NaOH (7.4 ml) as in Example 34, one obtains the crudetriazole derivative. Chromatography on silica gel (97:3 CH₂ Cl₂ :CH₃ OH)provides purified5-amino-1-[3-(trifluoromethyl)-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.

What is claimed is:
 1. A compound having the formula: ##STR6## wherein:##STR7## wherein one of R, R' and R" is trichlorovinyl and the other twoof R, R' and R" are selected from hydrogen, halogen, cyano,trifluoromethyl, loweralkanoyl, nitro, loweralkyl, loweralkoxy, carboxy,carbalkoxy, trifluoromethoxy, acetamido, loweralkylthio,loweralkylsulfinyl, loweralkylsulfonyl, trichlorovinyl,trifluoromethylthio, trifluoromethylsulfinyl, ortrifluoromethylsulfonyl;R₂ is amino, mono or diloweralkyl amino,acetamido, acetimido, ureido, formamido, formimido or guanidino; and R₃is carbamoyl, cyano, carbazoyl, amidino or N-hydroxycarbamoyl.
 2. Thecompound of claim 1 wherein one of R, R' and R" is trichlorovinyl andthe other two of R, R' and R" are selected from hydrogen, halogen,cyano, trifluoromethyl, trichlorovinyl or methyl;R₂ is amino and R₃ iscarbamoyl.
 3. The compound of claim 2 wherein:R is trichlorovinyl; R' ishydrogen, and R" is selected from halogen, cyano, trifluoromethyl ormethyl; R₂ is amino; and R₃ is carbamoyl.
 4. The compound of claim 1wherein R is trichlorovinyl, R' is hydrogen and R" is halogen.
 5. Thecompound of claim 1 which is5-amino-1-[3-chloro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.6. The compound of claim 1 which is5-amino-1-[3-bromo-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.7. The compound of claim 1 which is5-amino-1-[3-fluoro-5-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.8. The compound of claim 1 which is5-amino-1-[3-trifluoromethyl-5-trichlorovinylbenzyl]-1,2,3-triazole-4-carboxamide.9. The compound of claim 1 which is5-amino-1-[4-chloro-3-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.10. The compound of claim 1 which is5-amino-1-[3,5-dichloro-4-(trichlorovinyl)benzyl]-1,2,3-triazole-4-carboxamide.